JP2007516826A - Modified catalyst support - Google Patents

Abstract

A modified catalyst support that exhibits abrasion resistance and / or disassembly resistance is provided. A process is provided for making a modified catalyst support comprising treating the support slurry with a solution of monosilicic acid. A process is provided for using a catalyst comprising a modified catalytic unit pair in a Fischer-Tropsch synthesis. In one embodiment, a catalyst composition comprising the following: a support material having about 0.1 to about 10.6 Si deposited thereon per 1 nm ^{2 of} support surface area, wherein Si atoms There is provided a catalyst composition comprising a support, wherein is attached to a support material through an oxygen atom.

Description

  The present invention relates to a modified catalyst support that exhibits wear resistance and / or disassembly resistance and / or reproducibility. The invention further relates to a process for making a modified catalyst support. The invention further relates to the use of a Fischer-Tropsch catalyst comprising an abrasion resistant catalyst and / or a disassembly resistant and / or renewable support in Fischer-Tropsch synthesis.

(Background of the present invention)
Supported catalysts used in Fischer-Tropsch reactors (including, for example, slurry bubble column reactors and continuous stirred tank reactors (“CSTR”)) are subjected to agitation that causes significant impact and attrition forces . Such collisions and forces can cause damage mechanisms that can cause wear of the catalyst and / or catalyst support over time. Wear of the catalyst and / or catalyst support increases operating costs due to increased catalyst requirements. Furthermore, attrition produces fines that must be removed by filtration. The filtration process can result in loss of active catalyst in addition to fines removal, which can further increase operating costs.

  The catalyst support used in the fixed bed reactor can also be subjected to movement and collision during a batch or continuous regeneration process. As a result, some attrition can occur in the fixed bed reactor. In addition, catalyst supports (eg, shaped extrudates) often exhibit appreciable wear during catalyst production (eg, cobalt deposition on the support). In such cases, the abraded fines must be removed from the catalyst product prior to use to prevent reactor clogging.

  Attempts to reduce catalyst attrition include non-aqueous processes. Such a process is such that the silicateizing agent used reacts rapidly with water (this displaces the desired reaction of the silicate with hydroxyl or oxide groups on or near the surface of the catalyst support). So it requires the use of a non-aqueous solvent.

  Yet another known process uses an ethanol (ie, non-aqueous) solution of tetraethoxysilicate for the purpose of suppressing the solubility of the support in acidic aqueous solutions typically encountered during the preparation of supported catalysts. Then, silicon is deposited on the catalyst support.

  However, the use of non-aqueous solvents requires very specialized equipment for the commercial processing of flammable solvents and the cost of the solvent itself.

(Summary of the Invention)
Some embodiments of the present invention provide a catalyst composition comprising a support material on which is deposited about 0.1 to about 10.6 Si per nm ^{2 of} support surface area, wherein Si atoms Are bonded to the support material via oxygen atoms.

Another embodiment of the present invention provides a catalyst composition comprising a support material on which is deposited about 0.1 to about 10.6 Si per nm ^{2 of} support surface area, wherein Less than about 10 wt% is in polymer form.

  Yet another embodiment of the present invention provides a method of treating a catalyst support, the method comprising: contacting the support material with an anti-wear composition comprising monosilicic acid and thereby treated Providing a catalyst support.

  Yet another embodiment of the present invention provides a catalyst composition suitable for use in the Fisher-Tropsch process, which comprises a mixture or reaction product of: a wear material comprising a support material and monosilicic acid. A wear resistant support prepared by contacting with a suppressive composition; a catalyst precursor comprising cobalt and a first modifier selected from the group consisting of Ca, Sc, Ba, La, Hf, and combinations thereof A composition; and at least one activator selected from the group consisting of Ru, Rh, Pd, Re, Ir, Pt, and combinations thereof.

  Yet another embodiment of the present invention provides a Fisher-Tropsch product comprising: paraffin wax; and less than about 50 ppm gamma alumina particles having a diameter less than about 20 nm: wherein the concentration of gamma alumina particles is , Determined after primary filtration.

A first embodiment of the present invention provides a catalyst composition comprising: a catalyst composition comprising a support material on which is deposited about 0.1 to about 10.6 Si per nm ^{2 of} support surface area. Wherein an Si atom is bonded to the support material via an oxygen atom. In some such embodiments, silicon is deposited on the support material at a concentration between about 0.55 Si / nm ² and about 5.0 Si / nm ² . Alternatively, in some such embodiments, silicon is deposited on the support material at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ² . In some embodiments, the support material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, zirconia, Group III element refractory oxide, Group IV It is selected from the group consisting of elemental refractory oxides, group V element refractory oxides, group VI element refractory oxides, and group VIII element refractory oxides and mixtures thereof. In some embodiments, the carrier material is preformed. In a preferred embodiment, the support material is aggregated gamma alumina. In still other embodiments, the support material is alumina bonded titania. In some embodiments of the invention, the catalyst has been regenerated. Some embodiments of the catalyst composition include a group consisting of between about 12 wt% and about 30 wt% Co; between about 0.5 wt% and about 2 wt% Ca, Sc, Ba, La, and Hf. A first additive selected from; and a second addition selected from the group consisting of Ru, Rh, Pd, Re, Ir, and Pt between about 0.03 wt% and about 0.3 wt% An agent may further be included. In a preferred embodiment, the catalyst composition comprises between about 12 wt% and about 30 wt% Co; between about 0.5 wt% and about 2 wt% La; and between about 0.03 wt% and about 0.3 wt%. Further including Ru.

Another embodiment of the present invention provides a catalyst composition comprising a support material having deposited thereon from about 0.1 to about 10.6 Si / nm ² per nm ^{2 of} support surface area, wherein Less than about 10 wt% of silicon is in polymer form. In some embodiments of the invention, silicon is deposited on the support material at a concentration between about 0.55 Si / nm ² and about 5.0 Si / nm ² . In an alternative embodiment of the invention, silicon is deposited on the support material at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ² . In some embodiments of the present invention, the support material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, zirconia, a refractory oxide of a group III element, a group IV It is selected from the group consisting of elemental refractory oxides, group V element refractory oxides, group VI element refractory oxides, and group VIII element refractory oxides and mixtures thereof. In a preferred embodiment of the invention, the support material is aggregated gamma alumina. In some embodiments of the invention, the support material is alumina bonded titania. In certain embodiments of the invention, less than about 5 wt% of silicon is present in polymer form. In preferred embodiments, less than about 2.5 wt% of silicon is present in polymer form. In some embodiments of the invention, the catalyst has been regenerated. In a preferred embodiment, the carrier material is preformed. In still other preferred embodiments of the present invention, the catalyst composition comprises between about 12 wt% and about 30% Co; between about 0.5 wt% and about 2 wt% Ca, Sc, Ba, La, And a first additive selected from the group consisting of Hf and Hf; and selected from the group consisting of Ru, Rh, Pd, Re, Ir, and Pt between about 0.03 wt% and about 0.3 wt% A second additive. In the most preferred embodiment of the present invention, the catalyst composition comprises between about 12 wt% and about 30% Co; between about 0.5 wt% and about 2 wt% La; and between about 0.03 wt% and about 0.03 wt%. Further comprises Ru, between 0.3 wt%.

Another embodiment of the present invention provides a method of treating a catalyst support, the method comprising: contacting the support material with an anti-wear composition comprising monosilicic acid, thereby treating the treated catalyst Providing a carrier. In some embodiments, the treated catalyst support has a surface concentration between about 0.1 Si atoms / nm ² and about 10.60 Si atoms / nm ² . In one preferred embodiment, the anti-wear composition comprises between about 0.02% and about 5.4% Si by weight. In another preferred embodiment, the anti-wear composition comprises between about 0.2% and about 5.4% Si by weight. In yet other embodiments, the anti-wear composition is prepared by contacting the silicate with water under acidic conditions. In a preferred embodiment, the silicate comprises monosilicic acid. In still other embodiments, monosilicic acid is prepared by contacting tetraethoxysilane and water under acidic conditions. In some embodiments of the methods of the present invention, the silicate is sodium orthosilicate or sodium metasilicate, and the pH is about 1.5 to about 3.5 at a temperature in the range of about 0 ° C to about 5 ° C. It is a range. In yet other embodiments of the method of the present invention, the antiwear composition is added to the catalyst support at a temperature in the range of about 0 ° C to about 95 ° C. In certain preferred embodiments of the method of the present invention, the temperature ranges from about 0 ° C to about 10 ° C. In some embodiments of the methods of the present invention, the anti-wear composition comprises a polysilicic acid species, wherein the concentration of monosilicic acid is higher than the concentration of trisilicic acid and higher order silicic acid polymers. . In yet another embodiment of the method of the present invention, monosilicic acid is the predominant silicic acid species in the antiwear composition. In some embodiments of the method of the present invention, the carrier material is preformed.

  Yet another embodiment of the present invention provides a catalyst composition suitable for use in a Fischer-Tropsch process, which comprises the following mixture or reaction product: an anti-wear composition comprising a support material and monosilicic acid. A wear-resistant carrier prepared by contacting the product with a catalyst; a catalyst precursor composition comprising cobalt and a first modifier selected from the group consisting of Ca, Sc, Ba, La, Hf, and combinations thereof And at least one activator selected from the group consisting of Ru, Rh, Pd, Re, Ir, Pt, and combinations thereof; 37. The catalyst composition of claim 36, wherein the composition is substantially free of particles having a diameter of less than about 20 nm under typical Fisher-Tropsch reaction conditions. In some embodiments of catalyst compositions suitable for use in the Fisher-Tropsch process of the present invention, the support material comprises aggregated gamma alumina. In still other embodiments of catalyst compositions suitable for use in the Fisher-Tropsch process, the support material is preformed.

  Yet another aspect of the invention provides a Fisher-Tropsch product comprising: paraffin wax; and less than about 50 ppm gamma alumina particles having a diameter less than about 20 nm: wherein the concentration of gamma alumina particles is Determined after primary filtration. In certain embodiments of the Fisher-Tropsch product of the present invention, the Fisher-Tropsch product is made using a regenerated Fisher-Tropsch catalyst.

In yet another aspect of the present invention, a method is provided for reducing the occurrence and severity of catalyst attrition, wherein the method comprises the following steps: about 0.1 per ² nm of support surface area. Depositing 1 to about 10.6 Si on the catalyst support surface, wherein Si atoms are bonded to the support material via oxygen atoms. In still other embodiments of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the silicon is a support material at a concentration between about 0.55 Si / nm ² and about 5.0 / nm ^2. Deposited on top. In yet another embodiment of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the silicon is supported at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ^2. Deposited on the material. In yet another embodiment of the method for reducing the occurrence and severity of catalyst wear of the present invention, the support material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, Zirconia, Group III element refractory oxide, Group IV element refractory oxide, Group V element refractory oxide, Group VI element refractory oxide, Group VIII element refractory oxide, and these Selected from the group consisting of mixtures. In a preferred embodiment of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the support material is aggregated gamma alumina. In yet another embodiment of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the support material is alumina bonded titania.

Yet another aspect of the present invention provides a method for reducing the occurrence and severity of catalyst attrition comprising the following steps: from about 0.1 to about 10 per nm ^{2 of} support surface area. Depositing 6 Si on the surface of the catalyst support, wherein less than about 10 wt% silicon is in polymer form. In still other embodiments of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the silicon is a support material at a concentration between about 0.55 Si / nm ² and about 5.0 / nm ^2. Deposited on top. In yet another embodiment of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the silicon is supported at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ^2. Deposited on the material. In yet another embodiment of the method for reducing the occurrence and severity of catalyst wear of the present invention, the support material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, Zirconia, Group III element refractory oxide, Group IV element refractory oxide, Group V element refractory oxide, Group VI element refractory oxide, Group VIII element refractory oxide, and these Selected from the group consisting of mixtures. In a preferred embodiment of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the support material is aggregated gamma alumina. In yet another embodiment of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the support material is alumina bonded titania. In still other embodiments of the method for reducing the occurrence and severity of catalyst attrition of the present invention, the support material is present in polymer form with less than about 5 wt% of silicon. In a preferred embodiment of the method for reducing the occurrence and severity of catalyst wear of the present invention, less than about 2.5 wt% of silicon is in polymer form.

Another aspect of the present invention provides a method for reducing the occurrence and severity of catalyst support material disassembly comprising the following steps: from about 0.1 per 1 nm ^{2 of} support surface area Depositing approximately 10.6 Si on the surface of the catalyst support, wherein Si atoms are bonded to the support material via oxygen atoms. In still other embodiments of the method for reducing the occurrence and severity of catalyst support material disassembly of the present invention, the silicon is between about 0.55 Si / nm ² and about 5.0 / nm ² . Deposited on the support material at a concentration. In still other embodiments of the method for reducing the occurrence and severity of catalyst support material de-aggregation of the present invention, the silicon is between about 0.7 Si / nm ² and about 3.5 Si / nm ^2. Deposited on the support material at a concentration of In yet another embodiment of the method for reducing the occurrence and severity of catalyst support material desorption of the present invention, the support material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile. Titania, magnesia, zirconia, Group III element refractory oxide, Group IV element refractory oxide, Group V element refractory oxide, Group VI element refractory oxide, and Group VIII element refractory oxidation As well as a mixture thereof. In yet another embodiment of the method for reducing the occurrence and severity of catalyst support material de-aggregation of the present invention, the support material is aggregated gamma alumina. In yet another embodiment of the method for reducing the occurrence and severity of catalyst support material de-aggregation of the present invention, the support material is alumina-bound titania.

Yet another aspect of the invention provides a method for reducing the occurrence and severity of catalyst support material disassembly comprising the following steps: about 0.1 per 1 nm ^{2 of} support surface area Depositing about 10.6 Si on the catalyst support surface, wherein less than about 10 wt% of the silicon is in polymer form. In still other embodiments of the method for reducing the occurrence and severity of catalyst support material disassembly of the present invention, the silicon is between about 0.55 Si / nm ² and about 5.0 / nm ² . Deposited on the support material at a concentration. In still other embodiments of the method for reducing the occurrence and severity of catalyst support material de-aggregation of the present invention, the silicon is between about 0.7 Si / nm ² and about 3.5 Si / nm ^2. Deposited on the support material at a concentration of In yet another embodiment of the method for reducing the occurrence and severity of catalyst support material desorption of the present invention, the support material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile. Titania, magnesia, zirconia, Group III element refractory oxide, Group IV element refractory oxide, Group V element refractory oxide, Group VI element refractory oxide, and Group VIII element refractory oxidation As well as a mixture thereof. In a preferred embodiment of the method for reducing the occurrence and severity of catalyst support material de-aggregation of the present invention, the support material is aggregated gamma alumina. In yet another embodiment of the method for reducing the occurrence and severity of catalyst support material de-aggregation of the present invention, the support material is alumina-bound titania. In yet other embodiments of the method for reducing the occurrence and severity of catalyst support material of the present invention, less than about 5 wt% of silicon is present in polymer form. In yet another embodiment of the method for reducing the occurrence and severity of catalyst support material of the present invention, less than about 2.5 wt% of the silicon is in polymer form.

(Description of Embodiment of the Present Invention)
The term “support” means any preformed inorganic support material that has accessible hydroxyl and / or oxide groups and has penetrable pores. The carrier, as used herein, can have any shape. The holes typically have openings larger than about 5 nm across the largest axis.

  The term “preformed” is formed prior to treatment with a silicon compound and impregnation with an active metal such as a Group VIII metal, including, for example, extraction, washing, drying, and particle size setting. Catalyst support. Catalyst supports included in the term “preformed” include, for example, spray dried supports, extruded supports, and pelletized supports.

  The term “Fisher-Tropsch product” refers to the aggregate composition of hydrocarbons formed from synthesis gas by the FT synthesis process and remaining in the synthesis reactor as a liquid at process conditions.

  The term “primary filtration” means the filtration of the Fisher-Tropsch product as the Fisher-Tropsch product passes through the FT reactor and removes particles larger than about 5 μm.

  The term “paraffin wax” means a hydrocarbon composed primarily of unbranched —CH— chains that are semi-solid to solid at room temperature and room pressure.

  The term “directly bonded to the support material via an oxygen atom” means a bond via one or more single bonds to one or more oxygen atoms, each oxygen atom being bonded to a metal of the support material. It is connected with bond.

  In some embodiments of the process of the present invention, monosilicic acid (“MSA”) is prepared according to the teachings of US Pat. No. 2,588,389. In a preferred embodiment of the invention, MSA is done under conditions that minimize the polymerization of MSA. Such conditions are well known in the art and examples of such conditions are discussed in the references cited above. In some embodiments of the invention, the MSA is formed from the precursor at a pH between about 1.5 and about 3.5, a temperature between about 0 ° C. and about 5 ° C. In some embodiments, the MSA is formed from the precursor at a temperature up to about 25 ° C. In preferred embodiments, the MSA is formed from the precursor at a temperature between about 0 ° C. and about 8 ° C .; in the most preferred embodiment, the MSA is at a temperature between about 0 ° C. and about 5 ° C. Formed from precursors. The precursor can be any aqueous solution of a silicate (including sodium silicate, such as sodium orthosilicate and sodium metasilicate). MSA solutions typically contain from about 0.1% to about 1.0% Si by weight relative to the total solution. Following the formation of MSA, the MSA solution is preferably contacted with the support in the shortest possible time. MSAs are very reactive and readily form polymers by reaction with themselves or with other oxidizing surfaces (eg, the surface of a typical catalyst support). Contact of the MSA and catalyst support can occur by batch mixing or by metered addition of the MSA solution to an aqueous suspension of the support material. When batch mixing is used, the carrier solution is generally vigorously stirred during the addition of MSA to maximize contact between the MSA and the carrier particles. When metered addition is used, MSA is a rate that minimizes self-polymerization and maintains the reaction between MSA and support by maintaining a relatively low concentration of untreated MSA relative to the total solution. Is added. Nevertheless, the reaction between MSA and some catalyst support (eg, alumina) can be faster than MSA self-polymerization. In such cases, batchwise addition of MSA is used, and even if a higher concentration of MSA is present in the mixture, an approximately monolayer of silicon can be easily deposited on the support particles. The MSA and carrier mixture may be stirred (preferably vigorously stirred) during and / or after mixing to facilitate contact between the MSA and the surface of the carrier particles. In a preferred embodiment of the invention, the amount of water used to form an aqueous suspension of the carrier material is minimized and only the amount necessary to allow vigorous stirring is used. The amount of such water will vary according to the type, size and shape of the carrier used. Generally, the MSA solution can be contacted with the carrier for about 1 minute to 2 hours or more prior to subsequent processing. The MSA solution can be contacted with the support at a temperature in the range between about 0 ° C. and about 95 ° C.

  If higher temperatures are used, the MSA reagent can be added to the support slurry at a higher rate due to the faster reaction rate between the MSA and the support material. In addition, even at temperatures below 5 ° C., MSA reagents show some self-polymerization. Even with some degree of MSA self-polymerization, the activator in the MSA reagent / carrier slurry mixture appears to be predominantly in the monomeric form of silicic acid. Relatively rapid hydrolysis (ie, depolymerization) of low MSA polymers has been observed at low unreacted MSA concentrations. Even at the end of the MSA addition, the active monomer predominates when the concentration of unreacted silicate increases to about 500 ppm in the mixture.

  Following coupling of the MSA onto the support, the mixture can be cooled, excess solution can be decanted, and the treated support is washed with water to remove excess acid. The decantation-wash cycle can be repeated. Following the final decantation, the remaining dense slurry can be filtered prior to drying and calcining. The slurry is then dried and then calcined at a temperature in the range of about 400 ° C. to about 800 ° C., preferably about 600 ° C.

  The filter pore size used will generally depend on the size and shape of the support. In fact, the dense slurry does not need to be filtered, but rather can be subjected to any of a number of known techniques for dewatering the dense slurry. For example, the dense slurry can be centrifuged. Typically, the treated support material is dried at a temperature between about 100 ° C. and about 200 ° C., preferably at about 150 ° C., until the material is flowable. In commercial operation, it is understood that the dewatered slurry can be dried and fired continuously, with the front portion of the firing zone acting as a dryer by adjusting the temperature ramp and flow rate. In many applications, the support is maintained at the firing temperature for at least about 1 hour.

The terms “carrier” and “carrier material” are used interchangeably herein. Supports useful in the present invention can be of any shape (eg, substantially spherical or round) having accessible hydroxyl or oxide groups and penetrating pores necessary for use in Fisher-Tropsch synthesis. Including any preformed inorganic particles having an extrudate). Examples of suitable support materials include, for example, alumina (γ alumina, η alumina, θ alumina, δ alumina, and ρ alumina), anatase titania and rutile titania, magnesia, zirconia, or group III elements, group IV elements, V Other refractory oxides selected from group elements, group VI elements, and group VIII elements. Prior to treatment in accordance with the present invention, the support may have a diameter in the range of about 0.025 mm to about 0.2 mm or an equivalent diameter. The amount of Si bound to the support material can range between about 0.77 Si / nm ² to about 10.6 Si / nm ² .

As previously described, monosilicic acid (Si (OH) ₄ ) can self-polymerize with a degree of polymerization that depends on temperature, pressure and silicate concentration. As a result, the preparation of a practical solution of silicic acid can include not only silicic acid monomers but also higher order polymer forms. The most effective solutions for the purposes of the present invention are composed of higher order polymer forms with the lowest concentration. The quality of the solution prepared for the purposes of the present invention (ie, less polymer form, more monomer form, higher solution quality) can be attributed to the formation of aqueous silicon molybdate species, as is known in the art. Can be characterized using colorimetric determination based.

The extent of MSA polymerization can be monitored using spectroscopic techniques known in the art. One known spectroscopic method relies on the depolymerization of low molecular weight polymers of SiO ₂ and the formation of silicomolybdic acid having a yellow color. The reaction between Si (OH) ₄ and molybdic acid is very rapid. The formation rate of Si (OH) ₄ is inversely proportional to the length of the silicate polymer. Thus, the lower the degree of polymerization, the faster the solution will reach its final color intensity.

  Several tests were made using this spectroscopic technique where the color change was monitored using a spectrophotometer set at 410 nm. The MSA monomer reached its final color in less than 2 minutes. The MSA cubic octamer requires more than 10 minutes to reach its final color and shows less than 50% of its final color within the first 2 minutes. It should be noted that higher order polymers require an even longer time to show their final color intensity and show a correspondingly lower proportion of their color in less than 2 minutes. In some embodiments of the invention, the test solutions reached about 80% of their final color within 2 minutes and reached their final color within 6-10 minutes. A solution was considered suitable for use if> 90% of the final color developed within 5 minutes. In a preferred embodiment of the invention, the test solutions produced> 90% of their color within 2 minutes, indicating a very high monomer content at the start.

  The treated support can be used for the preparation of a catalyst, such as a Fisher-Tropsch catalyst. Any of a number of catalyst preparation methods (eg, VIII metal impregnation) are known in the art and may be utilized with the treated support.

  A Fisher-Tropsch catalyst incorporating the wear resistant catalyst support of the present invention has a catalytically active amount of catalytic metal (usually between about 1 wt% and 100 wt%, preferably between 2 wt% and 60 wt%, most preferably, Between about 10 wt% and about 30 wt%). Promoters and / or activators can be included in the catalyst composition, and promoters and activators useful in Fisher-Tropsch catalysts are well known in the art. Accelerators include, for example, ruthenium, rhenium, platinum, hafnium, cerium, and zirconium. The promoter and / or activator is usually present in an amount less than the amount of primary catalyst metal.

  One typical catalyst preparation method utilizes initial moisture impregnation. For example, the cobalt nitrate salt can be impregnated with initial moisture onto a titania support, silica support, or alumina support, followed by impregnation of an accelerator, if necessary. The catalyst can then be calcined at about 250 ° C. to about 500 ° C. to convert the metal salt to its corresponding oxide. The oxide is then treated by treatment with hydrogen or a hydrogen-containing gas at a temperature from about 300 ° C. to about 500 ° C. for a time sufficient to substantially reduce the oxide to a metal in elemental or catalytic form. Can be reduced. Other known catalyst preparation methods are described in U.S. Pat. Nos. 4,673,993; 4,717,702; 4,477,595; 4,663,305; 822,824; 5,036,032; 5,140,050; 5,252,613; and 5,292,705.

  A carrier treated as described herein exhibits improved abrasion resistance over an untreated carrier. One method for measuring the relative wear resistance of a carrier is to use an ultrasonic probe to create conditions that can cause carrier particles to collide with each other at a high frequency and with sufficient energy to cause grinding of the carrier particles. based on. Such a test method is discussed in US Pat. No. 6,262,132. FIG. 1 shows the results of such an ultrasonic test on a carrier (both first treated and untreated samples of such a carrier). The curve in FIG. 1 shows the cumulative volume% as a function of particle size for these samples before and after ultrasonic testing. Specifically, the curve indicated by the diamond data points represents the particle size accumulation distribution of the untreated carrier prior to sonication; the curve indicated by the triangle data points represents the first treatment prior to sonication. The curve indicated by the square data points represents the particle size accumulation distribution of the untreated carrier following sonication; the curve indicated by the “X” data points is Figure 2 shows the particle size accumulation distribution of a first treated carrier after sonication. As can be seen from FIG. 1, the untreated carrier shows a significantly greater migration to a smaller sonicated particle size than that exhibited by the treated carrier. The same trend can be seen in FIG. 2, showing that the untreated carrier after the ultrasound test moves significantly larger to a smaller particle size than the second treated carrier following the ultrasound test. The carrier material used in the embodiment shown in FIGS. 1 and 2 is the same material, but is another sample of such material. The untreated sample is the same in both FIGS. Referring to both FIGS. 1 and 2, the untreated carrier after the ultrasound test shows a population of particles less than 20 microns in diameter. Although the treated carrier after ultrasonic testing also exhibits particles having a diameter (or effective diameter) of less than 20 microns, the population of less than 20 microns in the treated carrier is in the amount found in the untreated carrier. About one-half. Furthermore, the overall transfer to smaller particle sizes is also less in the treated carrier than in the untreated carrier.

  The ultrasonic test discussed above is completed with an untreated carrier sample, and the% accumulated volume versus particle size of such a sample before and after the ultrasonic test is shown in FIG. The% accumulated volume versus particle size was then re-measured for untreated samples that were subjected to ultrasonic testing after 6 months. The particle size accumulation distribution remains substantially the same as the distribution measured in earlier tests, thereby indicating that the ultrasound test is very rigorous with excellent reproducibility.

In addition to the catalyst particles that wear away, it has been observed that the wax that is a Fisher-Tropsch product can also contain particles that are significantly smaller in size than the wear product. NMR analysis of these particles, according to known methods, shows that these solids consist essentially of gamma alumina crystals. Using known methods, TEM analysis of these particles has a size of less than about 20 nm along any crystal axis. Such γ-alumina crystals are considered to be disassembled fragments from the catalyst particles. Since the deassembled gamma alumina fragment is significantly smaller in size than the attrition product, the deassembled gamma alumina can be separated from the attrition product. The composition of the deassembled γ-alumina product is different from that of the original catalyst. Although the catalyst typically has a composition of about 20 wt% elemental cobalt and 70 wt% Al ₂ O ₃ , the de-aggregated γ-alumina product has reduced cobalt, typically about 3 wt% to About 4 wt% elemental Co and about 95 wt% Al ₂ O ₃ are included.

(Example 1-Preparation of catalyst sample 1)
An MSA reagent solution was prepared by rapidly adding 94.9 g TEOS to 4 L acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. Aliquots were removed 15 minutes after TEOS addition and the rate of color change was tested. Over 90% of the full color developed within 5 minutes. In a separately stirred heating vessel, an alumina carrier slurry containing 640 g of alumina suspended in 2 L of demineralized water was heated. The slurry was maintained at 50 ° C. ± 5 ° C. throughout the addition of the MSA reagent, which was added at a rate of 35 ml / min. Following completion of the MSA addition, the slurry was stirred and maintained at 50 ° C. ± 5 ° C. until> 95% of the silicon reacted with the alumina. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried overnight in an oven maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 200 g of the Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.5 g of this saturated Co solution was used for the first impregnation pass. 6.25g of La a _{(NO 3) 3 · 6H 2} O was dissolved in demineralized water 20g, combined with the Co solution. The amount of solution was selected to produce an initial wet powder when applied to the carrier in a rotating vessel. The impregnated powder is tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. The powder is cooled to room temperature, weighed and transferred to a shallow baking dish so that the powder depth is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 187 g of saturated cobalt solution, add 1.8 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . The second impregnation solution is again applied to the substrate in the tumbling impregnator, dried and fired as after the first pass.

(Example 2-Preparation of catalyst sample 2)
An MSA reagent solution was prepared by rapidly adding 73.6 g TEOS to 667 mL acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. Aliquots were removed 15 minutes after TEOS addition and the rate of color change was tested. Over 90% of the full color occurred within 5 minutes. In a separately stirred heating vessel, an alumina support slurry containing 100 g of alumina suspended in 333 mL of demineralized water was heated. The slurry was maintained at 50 ° C. ± 5 ° C. throughout the addition of the MSA reagent, which was added at a rate of 5 ml / min. Following completion of the MSA addition, the slurry was stirred and maintained at 50 ° C. ± 5 ° C. until> 95% of the silicon reacted with the alumina. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried for 6 hours in a static muffle furnace maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 93.8 g of the Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 87.6 g of this saturated Co solution was used for the first impregnation pass. Was dissolved 4.08g of La a _{(NO 3) 3 · 6H 2} O in demineralized water 10 g, in combination with Co solution. The amount of solution is selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder is tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. The powder is cooled to room temperature, weighed and transferred to a shallow baking dish so that the powder depth is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 87.5 g of saturated cobalt solution, add 0.97 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . The second impregnation solution is again applied to the substrate in the tumbling impregnator, dried and fired as after the first pass.

(Example 3-Preparation of catalyst sample 3)
An MSA reagent solution was prepared by rapidly adding 94.9 g TEOS to 4 L acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. An aliquot was removed 15 minutes after the addition of TEOS and the rate of color change was tested. Over 90% of the full color occurred within 5 minutes. A slurry of alumina support containing 640 g of alumina suspended in 2 L of demineralized water was added to the MSA. The mixture was heated to 50 ° C. ± 5 ° C. The mixture was stirred and maintained at 50 ° C. ± 5 ° C. until> 95% of the silicon reacted with the alumina. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried overnight in an oven maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 200 g of the Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.5 g of this saturated Co solution was used for the first impregnation pass. 6.25 g La (NO ₃ ) ₃ · 6H ₂ O was dissolved in 20 g demineralized water and combined with the Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder is tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 187 g of saturated cobalt solution, add 1.8 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . The second impregnation solution is again applied to the substrate in the tumbling impregnator, dried and fired as after the first pass.

(Example 4-Preparation of catalyst sample 4)
An MSA reagent solution was prepared by rapidly adding 38 g of TEOS to 1.62 L of acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. An aliquot was removed 15 minutes after the addition of TEOS and the rate of color change was tested. Full color above 90% occurred within 5 minutes. The MSA solution continued to cool and was maintained for about 60 hours. A slurry of alumina support containing 640 g of alumina suspended in 768 ml of demineralized water was added to the MSA. The mixture was heated to 50 ° C. ± 5 ° C. The mixture was stirred and maintained at 50 ° C. ± 5 ° C. until> 95% of the silicon reacted with the alumina. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried overnight in an oven maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 200 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.5 g of this saturated Co solution was used for the first impregnation pass. 6.25 g La (NO ₃ ) ₃ · 6H ₂ O was dissolved in 20 g demineralized water and combined with the Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 194 g of saturated cobalt solution, add 1.82 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . The second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

(Example 5-Preparation of catalyst sample 5)
An MSA reagent solution was prepared by rapidly adding 38 g of TEOS to 1.62 L of acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. An aliquot was removed 15 minutes after the addition of TEOS and the rate of color change was tested. Full color above 90% occurred within 5 minutes. A slurry of alumina support containing 640 g of alumina suspended in 768 ml of demineralized water was added to the MSA. The mixture was heated to 50 ° C. ± 5 ° C. The mixture was stirred until> 95% silicon reacted with the alumina and maintained at 50 ° C. ± 5 ° C. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried overnight in an oven maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 200 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.5 g of this saturated Co solution was used for the first impregnation pass. 6.25 g La (NO ₃ ) ₃ · 6H ₂ O was dissolved in 20 g demineralized water and combined with the Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 192 g saturated cobalt solution, add 1.82 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . This second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

Example 6 Preparation of Catalyst Sample 6
An MSA reagent solution was prepared by rapidly adding 94.9 g TEOS to 4 L acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to bring the pH between 2.2 and 2.5 and maintained at room temperature to 22 ° C. An aliquot was removed 15 minutes after the addition of TEOS and the rate of color change was tested. Full color above 90% occurred within 5 minutes. 640 g of alumina was added to the MSA. The mixture was heated to 50 ° C. ± 5 ° C. The mixture was stirred until> 95% silicon reacted with the alumina and maintained at 50 ° C. ± 5 ° C. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried overnight in an oven maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 200 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.5 g of this saturated Co solution was used for the first impregnation pass. 6.25 g La (NO ₃ ) ₃ · 6H ₂ O was dissolved in 20 g demineralized water and combined with the Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 187 g of saturated cobalt solution, add 1.8 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . This second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

Example 7-Preparation of catalyst sample 7
An MSA reagent solution was prepared by rapidly adding 89.3 g TEOS to 2 L acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. An aliquot was removed 15 minutes after the addition of TEOS and the rate of color change was tested. Full color above 90% occurred within 5 minutes. In a separate stirred and heated vessel, an alumina carrier slurry containing 300 g of alumina suspended in 1 L of demineralized water was heated. The slurry was held at 50 ° C. ± 5 ° C. throughout the addition of the MSA reagent, which was added at a rate of 15 ml / min. After completion of the MSA addition, the slurry was stirred and maintained at 50 ° C. ± 5 ° C. until> 95% silicon reacted with the alumina. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried for 6 hours in a static muffle furnace maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 200 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.5 g of this saturated Co solution was used for the first impregnation pass. 6.25 g La (NO ₃ ) ₃ · 6H ₂ O was dissolved in 20 g demineralized water and combined with the Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 185 g of saturated cobalt solution, add 1.78 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . The second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

Example 8-Preparation of catalyst sample 8
An MSA reagent solution was prepared by rapidly adding 68 g TEOS to 2 L acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. An aliquot was removed 15 minutes after the addition of TEOS and the rate of color change was tested. Full color above 90% occurred within 5 minutes. In a separate stirred heating vessel, an alumina support slurry containing 300 g of alumina suspended in 1 L of demineralized water was heated. The slurry was heated to 50 ° C. ± 5 ° C. during the addition of the MSA reagent, which was added at a rate of 15 ml / min. After completion of the MSA addition, the slurry was stirred and maintained at 50 ° C. ± 5 ° C. until> 95% silicon reacted with the alumina. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried for 6 hours in a static muffle furnace maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 200 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.5 g of this saturated Co solution was used for the first impregnation pass. 6.25 g La (NO ₃ ) ₃ · 6H ₂ O was dissolved in 20 g demineralized water and combined with the Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 188 g saturated cobalt solution, add 1.78 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . The second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

Example 9-Preparation of catalyst sample 9
An MSA reagent solution was prepared by rapidly adding 27.8 g TEOS to 1.33 L acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. An aliquot was removed 15 minutes after the addition of TEOS and the rate of color change was tested. Full color above 90% occurred within 5 minutes. The MSA solution continued to cool and was maintained for about 60 hours. In a separate stirred heating vessel, a slurry of the alumina support containing 200 g of alumina suspended in 667 ml of demineralized water was heated. The slurry was heated to 50 ° C. ± 5 ° C. during the addition of the aged MSA reagent, which was added at a rate of 15 ml / min. The mixture was stirred until> 95% silicon reacted with the alumina and maintained at 50 ° C. ± 5 ° C. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried for 6 hours in a static muffle furnace maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 160 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 138 g of this saturated Co solution was used for the first impregnation pass. 5.00g of La a _{(NO 3) 3 · 6H 2} O was dissolved in demineralized water 15 g, in combination with Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 151 g of saturated cobalt solution, 1.44 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ is added. The second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

Example 10-Preparation of catalyst sample 10
An MSA reagent solution was prepared by rapidly adding 29.8 g TEOS to 267 ml acidified demineralized water with vigorous stirring. Sufficient HNO ₃ was added to the water to maintain the pH between 2.2 and 2.5 and between 3 ° C. and 8 ° C. An aliquot was removed 15 minutes after the addition of TEOS and the rate of color change was tested. Full color above 90% occurred within 5 minutes. In a separate stirred heating vessel, a slurry of the alumina support containing 200 g of alumina suspended in 667 ml of demineralized water was heated. The slurry was heated to 50 ° C. ± 5 ° C. during the addition of the MSA reagent, which was added at a rate of 15 ml / min. After completion of the MSA addition, the slurry was stirred and maintained at 50 ° C. ± 5 ° C. until> 95% silicon reacted with the alumina. Once the reaction was complete, stirring was stopped, the solid was allowed to settle, and the clear mother liquor was decanted from the vessel. The remaining thick slurry was vacuum filtered to remove the rest of the solution. The filtered solid was spread on a drying tray to a thickness of less than 1.5 cm and dried for 6 hours in a static muffle furnace maintained at 140 ° C. The dry powder was then baked in a dish at 600 ° C. for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 200 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.5 g of this saturated Co solution was used for the first impregnation pass. 6.25 g La (NO ₃ ) ₃ · 6H ₂ O was dissolved in 20 g demineralized water and combined with the Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven that is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 184 g of saturated cobalt solution, add 1.78 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . The second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

  The catalysts made in Examples 1-10 were tested for abrasion resistance according to the following method. The catalyst was activated using hydrogen gas, and 20 cc of the activated catalyst was placed in a 0.5 L CSTR, with synthesis conditions of 410 ° F., 300 psi, GHSV 8000 / hr and agitator speed of 1000 rpm. After 50 hours of the synthesis operation, the conditions are adjusted to an agitator speed of 420 ° F., 400 psi, GHSV 8000 / hr and 2000 rpm. This condition is maintained for 150 hours. Upon completion of the CSTR wear test, the reactor is switched to a nitrogen purge and cooled to about 250 ° F. Maintain under these conditions for about 24 hours, during which time the entire catalyst and larger attrition fragments settle to the bottom of the reactor, while the fine attrition fragments remain suspended in the wax. The wax is then cooled to a solid and removed from the reactor as a single plug. The precipitated fraction of catalyst-containing wax can be separated from the overhead wax, which contains smaller attrition catalyst fragments that do not settle. Once separated, the overhead wax fraction is ground and homogenized, after which a representative sample is obtained. This representative fraction is placed in a Pyrex® beaker and placed in an oven maintained between about 280 ° F. and about 320 ° F. and allowed to melt. A Pyrex® filtration system equipped with a vacuum receiver is also heated to oven temperature. The wax is first filtered through a 5 μm filter, then the collected liquid is filtered through a 0.45 μm filter, and the collected liquid is finally filtered through a 0.1 μm filter. In each stage of filtration, a small amount of clean isopar solvent is used to clean all of the material from the bottom of the container. At the end of the filtration, the filtrate residue solid content is determined by ashing. The filtered solid is separated from the filter paper using a solvent in an ultrasonic bath. The solid-containing solvent is centrifuged to concentrate the solid, which is finally collected, dried and weighed. These lumps are referenced to the original lumps of catalyst placed in the reactor and the results are shown in the table contained in FIG.

(Example 11-Reaction of MSA with alumina)
667 ml of demineralized water was acidified to pH = 2.0 using HNO ₃ and cooled to below 8 ° C. using an ice bath. 74.63 g of TEOS was added to the acidified water with vigorous stirring. The rate of color change was tested after 15 minutes of mixing and showed> 90% of maximum color within 5 minutes. In a separate vessel, 333 ml of demineralized water was combined with 100 g of Sasol Chemical SCCa-30 / 140 alumina and heated to 50 ° C. while mixing with an overhead mixer. The silicic acid reagent was added to the alumina slurry using a peristaltic pump over 135 minutes. After 3 hours of stirring, the amount of unreacted silicic acid was found to be 35% of the initial charge. Care must be taken in this measurement to allow the depolymerization of somewhat larger polymers of silicic acid. This higher degree of polymerization results from a higher concentration of unreacted silicic acid, elevated temperature, and pH shift from optimal solubility in saturated preparation. The resulting sediment was self-limiting to about 5.7% on calcined alumina.

(Comparative Example 1-Reaction of MSA with silica)
667 ml of demineralized water was acidified to pH = 2.0 using HNO ₃ and cooled to below 8 ° C. using an ice bath. 13.9 g of TEOS was added to the acidified water with vigorous stirring. The rate of color change was tested after 15 minutes of mixing and showed> 90% of maximum color within 5 minutes. In a separate container, 333 ml of demineralized water was combined with 100 g of silica gel (Davisil Grade 64b Type 150a, available from Davision Catalysts) and heated to 50 ° C. while mixing in an overhead mixer. A background test of silicic acid formed in the slurry was performed using the molybdate acid color change test. The silicic acid reagent was added to the silica slurry using a peristaltic pump over 60 minutes. After mixing for 1 hour, an initial test of unreacted silica was performed. From this test, it was determined that the background color change from silica in the water slurry contributed less than 5% of the total color change at this point. The amount of remaining unreacted silicic acid was determined every hour for a total of 3 hours, at which time 75% of the silicic acid remained unreacted in the solution. The resulting precipitate was self-limiting to less than 0.5% on the calcined alumina.

(Comparative Example 2—Reaction of MSA with titania)
667 ml of demineralized water was acidified to pH = 2.0 using HNO ₃ and cooled to below 8 ° C. using an ice bath. 13.9 g of TEOS was added to the acidified water with vigorous stirring. The rate of color change was tested after 15 minutes of mixing and showed> 90% of maximum color within 5 minutes. In a separate container, 333 ml of demineralized water was combined with 100 g of titania (Titania Type P-25, available from Degussa AG) and heated to 50 ° C. with mixing in an overhead mixer. The silicic acid reagent was added to the titania slurry using a peristaltic pump over 60 minutes. After 1 hour of mixing, an initial test of unreacted silica was performed 1 hour after mixing and showed that 57% of the silicic acid remained unreacted. After 3 hours of mixing, the amount of unreacted silicic acid was found to be 36% of the original charge. The resulting precipitate was slightly self-limiting at 1% or less on calcined alumina.

(Comparative Example 3 and Example 11A—Deassembled γ Alumina)
A catalyst test factory batch, Example 11A, was prepared on Sasol Chemical SCCa-30 / 140 alumina modified to contain 3.0 Si / nm ² . A test factory batch of catalyst, Comparative Example 3, was prepared on unmodified Sasol Chemical SCCa-30 / 140 alumina. Example 11A was performed in a proprietary Fisher-Tropsch synthesis in a 36 inch bubble column reactor. Three runs using Comparative Example 3 were performed one each in 42 inch, 36 inch, and 6 inch slurry bubble columns using a dedicated Fischer-Tropsch synthesis. A wax sample was obtained at the filtered product outlet and analyzed for de-aggregated alumina at a comparative time with 45 days of steam. The results are given in Table 1 below. Deassembled γ alumina particles were separated from other Fischer-Tropsch catalyst attrition solids using a continuous filtration method. The wax sample is placed in a Pyrex® beaker and placed in an oven maintained between about 280 ° F. and about 320 ° F. and allowed to melt. A Pyrex® filtration system equipped with a vacuum receiver is also heated to oven temperature. The molten wax is continuously subjected to a series of continuous filtrations using 5 μm, 0.45 μm, and 0.1 μm pass filters. Initial filtration was performed using an Anodisc aluminum oxide filter membrane with a 0.02 μm passage size. At each stage of filtration, a small amount of clean Isopar solvent is used to clean all of the material from the bottom of the container. It was then incinerated according to the final filtrate ASTM-486 and the deaggregated particle content was determined.

（実施例１２−アルミナビーズ内のＳｉの分布）
名称ＳＣＣａ−３０／１４０で販売されるＳａｓｏｌ Ｃｈｅｍｉｃａｌから得られるアルミナ担体は、直径が２５μｍと１００μｍとの間の回転楕円体粒子からなる噴霧乾燥材料である。一ケイ酸試薬での処理後の担体粒子内または担体粒子上のＳｉのプロフィールを決定するために、改変担体のサンプルを、顕微鏡スライドに載せたポリマーマトリックス内に埋め込み、粒子全体の露出された断面をあらわにするように研磨した。次いで、研磨したスライドをＳＥＭを用いて調べ、いくつかのビーズの直径に沿って断片をエネルギー分散Ｘ線分析を使用して分析した。異なる直径の多くのビーズにわたって測定した場合、Ｓｉ／Ａｌシグナル比が、この技術の予想される変動とおよそ一致して、約１０％で変動することが見出された。数個のビーズについて数個の点の平均に基づいて、約１５％のわずかに高いＳｉ／Ａｌ比が、ビーズの極限の外部縁部で観測された。これらの観察から、本発明者らは、一ケイ酸とアルミナ表面との間の反応の速度が、ビーズ内の全ての点への試薬の拡散を可能にするのに十分な遅さであることを結論付けた。

(Example 12-Distribution of Si in alumina beads)
The alumina support obtained from Sasol Chemical sold under the name SCCa-30 / 140 is a spray-dried material consisting of spheroidal particles having a diameter between 25 and 100 μm. In order to determine the profile of Si in or on the carrier particles after treatment with a monosilicate reagent, a sample of the modified carrier is embedded in a polymer matrix mounted on a microscope slide and the exposed cross section of the whole particle Polished to reveal. The polished slides were then examined using SEM and fragments were analyzed using energy dispersive x-ray analysis along several bead diameters. When measured across many beads of different diameters, it was found that the Si / Al signal ratio varied by about 10%, approximately in line with the expected variation of this technique. A slightly higher Si / Al ratio of about 15% was observed at the extreme outer edge of the beads, based on an average of several points for several beads. From these observations, the inventors have shown that the rate of reaction between monosilicic acid and the alumina surface is slow enough to allow diffusion of the reagent to all points within the bead. I concluded.

Example 13-Surface Si Concentration in Polymerized Silicate Reagent
Prior to any further processing to form catalyst particles, the supports made by the methods of Examples 4 and 5 were analyzed using X-ray photoelectron spectroscopy (XPS). Each of the supports of Examples 4 and 5 was modified to give 0.8% Si on the fired support. The modified support of Example 5 was prepared immediately upon preparation of the MSA reagent, but the MSA used to make the modified support of Example 4 was about 60 hours before reacting with the alumina support. Initially aged. The rate of color change of the aged solution used to prepare the modified support of Example 4 indicated that the silica was polymerized to a very high degree. XPS is very surface sensitive and provides information about the surface in a layer about 5 nm deep. The catalyst beads were examined without replenishment preparation to limit the analysis to only the true outer surface of the beads. The Si / Al signal ratio was found to be 60% higher in the modification of Example 4 itself than in the modified support of Example 5, which means that the polymerized silicic acid is supported before the reaction with the alumina. Indicates that the entire particle could not be penetrated. As can be seen in the table of FIG. 4, the modified carrier of Example 4 was less effective than the modified carrier of Example 5 in mitigating attrition.

Example 14-Holding Abrasion Resistance with Regeneration
200 g of Sasol Puralox SCCa-30 / 140 alumina was placed in an impregnation vessel with a steam jacket. 37.04 g TEOS was added to 75 cc ethanol. The TEOS / EtOH mixture was added dropwise into the impregnation vessel. This mixture was mixed for 1 hour at room temperature. Steam drying was started and continued for 3 hours. The alumina mixture was cooled and then transferred to a ceramic baking dish. The depth of the alumina bed was <1.5 cm. The alumina was placed in a static muffle furnace and raised to 140 ° C. over about 30 minutes. The alumina was maintained at 140 ° C. for 2 hours. Subsequently, this dry powder was raised to 600 ° C. and baked for 4 hours. This support material contained 2.5 Si / nm ² .

The catalyst was prepared to have a nominal composition of 20% Co, 1% La, and 0.1% Ru in the calcined form. 100 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 70.8 g of this saturated Co solution was used for the first impregnation pass. Was dissolved 3.13g of La a _{(NO 3) 3 · 6H 2} O in demineralized water 10 g, in combination with Co solution. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven, which is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 106.7 g saturated cobalt solution, add 0.9 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ . The second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

  As described above in this example, the first 80 cc charge of the catalyst prepared on the TEOS / EtOH treated support is performed at 1 liter CSTR under typical FT synthesis conditions, and more than 55% Temperature and GHSV were adjusted to maintain conversion. After an initial working time of 2000 hours, it was regenerated according to the procedure described in US Pat. No. 6,812,179. The recharged recharged product was worked again for 2000 hours and regenerated again. Following a third working time of 2000 hours, the catalyst was recovered, dewaxed, and the particle size distribution was measured. The initial packed catalyst had a distribution with> 99% particles larger than 20 μm in diameter. After 6000 working hours and 2 regenerations, the recovered catalyst showed no detectable fines and still had> 99% particles larger than 20 μm.

The first 80 cc charge of the catalyst prepared on the MSA-treated support to deposit 3.0 Si / nm ² was performed with 1 liter CSTR under typical FT synthesis conditions, 55% In order to maintain the above conversion, the temperature and GHSV were adjusted. After an initial working time of 2000 hours, it was regenerated according to the procedure described in US Pat. No. 6,812,179. The recharged recharged product was worked again for 2000 hours and regenerated again. Following a third working time of 1800 hours, the catalyst was recovered, dewaxed, and the particle size distribution was measured. The initial packed catalyst had a distribution with> 99% particles larger than 20 μm in diameter. After 5800 working hours and 2 regenerations, the recovered catalyst showed no detectable fines and still had> 99% particles larger than 20 μm.

(Example 15-Preparation of catalyst sample 15 (TEOS / EtOH method))
350 g of Sasol SCCa-30 / 140 alumina was placed in an impregnation vessel with a steam jacket. 25.9 g TEOS was added to 168 cc ethanol. The TEOS / EtOH mixture was added dropwise into the impregnation vessel. This mixture was mixed for 1 hour at room temperature. Steam drying was started and continued for 3 hours. The alumina mixture was cooled and then transferred to a ceramic baking dish. The depth of the alumina bed was <1.5 cm. The alumina was placed in a static muffle furnace and raised to 140 ° C. over about 30 minutes. The alumina was maintained at 140 ° C. for 2 hours. Subsequently, this dry powder was raised to 600 ° C. and baked for 4 hours.

The catalyst was prepared to have a nominal composition of 20% Co and 0.1% Ru in the calcined form. 200 g Si modified catalyst support was placed in a rotary impregnation vessel with a steam jacket. A saturated solution prepared from Co (NO ₃ ) ₂ · 6H ₂ O and demineralized water was prepared previously. 172.45 g of this saturated Co solution was used for the first impregnation pass. The amount of solution was selected to produce an initial wet powder when added to the carrier in a rotating vessel. The impregnated powder was tumbled in an impregnator for 1 hour at ambient temperature and then steam dried for 3 hours. Cool the powder to room temperature, weigh and transfer to a shallow baking dish so that the depth of the powder is ≦ 2 cm. The dish is placed in an electric heating oven that is raised from ambient temperature to 120 ° C., maintained at 120 ° C. for 2 hours, raised to 350 ° C. over 2 hours, and maintained at 350 ° C. for an additional 2 hours. After cooling to ambient temperature, the calcined powder is again transferred to the impregnation vessel. To a second charge of 176.67 g saturated cobalt solution, 1.75 g of 13.5% Ru solution of Ru (NO) (NO ₃ ) ₃ is added. The second impregnation solution was again applied to the substrate in the tumbling impregnator, dried and fired to follow the first pass.

Example 16-Dispersion of Si on alumina surface via XPS
As silicic acid tends to polymerize, problems arise with the possibility of higher order oligomers beginning to form as the concentration of Si on the alumina surface increases. X-ray photoelectron spectroscopy (XPS) can be used differently to address this problem. Since the signal observed by XPS comes from the outermost surface exposed to the excitation x-ray beam (usually 3-5 nm deep), it is well suited to detect such changes in morphology . Even when the unit layer structure converts to a two layer structure, the signal of the second layer is attenuated compared to the signal from the first layer. As a result, the observed ratio of Si / Al as a function of surface coverage is detected as a layered structure morphology even when these layered structures are islands and not continuous surfaces. The deviation toward decreasing Si / Al is shown.

  Since XPS is very surface sensitive, it is necessary that the internal surface of the support be available for analysis. This was achieved by mechanical grinding of the calcined support followed by sieving through a 20 μm open sieve. Particles pulverized smaller than this dimension must expose a relatively high percentage of the internal surface.

FIG. 5 shows the change in Si / Al ratio observed for samples with nominal Si loading in the range of 0.3 Si / nm ^{2 to} 6.2 Si / nm ² . The high degree of linearity is clearly the same as the morphology of the SiO ₂ entity formed at the lowest 0.3 Si / nm ² with the highest concentration of 6.2 Si / nm ^2. It shows that. These observations indicate that the deposited SiO ₂ is most likely to bind as a single layer of individual entities on the Al ₂ O ₃ surface.

Example 17-Textual evidence for uniform deposition
Nitrogen adsorption can be used to monitor changes in surface area, pore volume, and average pore diameter as a function of Si loading on the alumina surface. As the polymer entity begins to form, pore blockage can occur, resulting in a discontinuous change in pore volume with increased loading. The following table shows the texture data obtained with several different nominal Si loadings. All three texture parameters show continuous behavior (especially average pore diameter), consistent with the continuous deposition of SiO ₂ on the alumina surface.

本発明が制限された数の実施例を用いて記載されているものの、これらの特定の実施形態は、本明細書中においてそれ以外で記載および特許請求される発明の範囲を制限することは意図されない。記載される実施形態からの改変および変更が存在する。当業者は、半導体材料形成プロセスのためのパラメーターが、例えば、温度、圧力、気流速度などで変化し得ることを認識する。従って、一組のプロセス条件下での選択基準を満たさない材料は、それにもかかわらず、別のセットのプロセス条件下での発明の実施形態において使用され得る。さらなる要素の組み込みは、そうでなければ可能でない有利な特性を生じ得る。また、プロセスが１つ以上の工程を含むように記載されているものの、これらの工程が、他に示されない限り、任意の順序の配列で実行され得ることが理解されるべきである。これらの工程は、組み合わされ得るかまたは分離され得る。最後に、本明細書中に開示される任意の数は、用語「約」または「およそ」が数を記載する際に使用されているか否かにかかわらず、近似を意味するように解釈されるべきである。添付の特許請求の範囲は、このような変更および改変を、本発明の範囲内として網羅することを意味する。

Although the invention has been described using a limited number of examples, these specific embodiments are intended to limit the scope of the invention otherwise described and claimed herein. Not. There are modifications and variations from the described embodiments. One skilled in the art will recognize that parameters for the semiconductor material formation process can vary, for example, with temperature, pressure, air velocity, and the like. Thus, materials that do not meet the selection criteria under one set of process conditions can nevertheless be used in embodiments of the invention under another set of process conditions. The incorporation of further elements can produce advantageous properties that would otherwise not be possible. It should also be understood that although the process is described as including one or more steps, these steps may be performed in any order of sequence unless otherwise indicated. These steps can be combined or separated. Finally, any number disclosed herein is to be interpreted as an approximation, regardless of whether the term “about” or “approximately” is used in the description of a number. Should. The appended claims are intended to cover such changes and modifications as fall within the scope of the invention.

FIG. 1 is a graph of cumulative volume% by particle size for an untreated carrier, a first treated carrier before sonication, and a first treated carrier after sonication. FIG. 2 is a graph of cumulative volume% by particle size for an untreated carrier, a second treated carrier before sonication, and a second treated carrier after sonication. FIG. 3 is a graph of cumulative volume% by particle size for an untreated carrier before sonication and an untreated carrier after sonication. FIG. 4 is a chart showing the characteristics of the catalysts considered in Examples 1-10. FIG. 5 is a graph showing the ratio of Si XPS intensity to Al XPS intensity.

Claims (71)

A catalyst composition comprising:
A support material having about 0.1 to about 10.6 Si deposited thereon per 1 nm ^{2 of} support surface, wherein Si atoms are bonded to the support material via oxygen atoms ,
A catalyst composition comprising: The catalyst composition of claim 1, wherein the silicon is deposited on a support material at a concentration between about 0.55 Si / nm ² and about 5.0 Si / nm ^2. Composition. The catalyst composition of claim 1, wherein the silicon is deposited on a support material at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ^2. Composition. The catalyst composition according to claim 1, wherein the carrier material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, zirconia, group III, group IV, V A catalyst composition selected from the group consisting of refractory oxides of elements of Groups III, VI and VIII and mixtures thereof. The catalyst composition according to claim 4, wherein the support material is aggregated γ-alumina. The catalyst composition according to claim 4, wherein the support material is alumina-bound titania. The catalyst composition according to claim 1, wherein the catalyst is regenerated. The catalyst composition according to claim 1, wherein the support material is formed in advance. The catalyst composition of claim 1, further comprising:
Between about 12 wt% and about 30% Co;
A first additive selected from the group consisting of between about 0.5 wt% and about 2 wt% Ca, Sc, Ba, La, and Hf;
A second additive selected from the group consisting of Ru, Rh, Pd, Re, Ir, and Pt between about 0.03 wt% and about 0.3 wt%;
A catalyst composition comprising: The catalyst composition of claim 1, further comprising:
Between about 12 wt% and about 30% Co;
La between about 0.5 wt% and about 2 wt%; and Ru between about 0.03 wt% and about 0.3 wt%,
A catalyst composition comprising: A catalyst composition comprising:
A support material having about 0.1 to about 10.6 Si deposited thereon per 1 nm ^{2 of} support surface, wherein less than about 10 wt% silicon is in polymeric form,
A catalyst composition comprising: 12. The catalyst composition of claim 11, wherein the silicon is deposited on a support material at a concentration between about 0.55 Si / nm ² and about 5.0 Si / nm ^2. Composition. 12. The catalyst composition of claim 11, wherein the silicon is deposited on a support material at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ^2. Composition. The catalyst composition according to claim 11, wherein the carrier material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, zirconia, group III, group IV, V A catalyst composition selected from the group consisting of refractory oxides of elements of Groups III, VI and VIII and mixtures thereof. The catalyst composition according to claim 14, wherein the support material is aggregated γ-alumina. 15. The catalyst composition according to claim 14, wherein the support material is alumina bonded titania. 11. The catalyst composition of claim 10, wherein less than about 5 wt% silicon is in polymer form. 11. The catalyst composition of claim 10, wherein less than about 2.5 wt% silicon is in polymer form. The catalyst composition according to claim 10, wherein the catalyst is regenerated. The catalyst composition according to claim 10, wherein the support material is formed in advance. The catalyst composition according to claim 10, further comprising:
Between about 12 wt% and about 30% Co;
A first additive selected from the group consisting of between about 0.5 wt% and about 2 wt% Ca, Sc, Ba, La, and Hf;
A second additive selected from the group consisting of Ru, Rh, Pd, Re, Ir, and Pt between about 0.03 wt% and about 0.3 wt%;
A catalyst composition comprising: The catalyst composition according to claim 10, further comprising:
Between about 12 wt% and about 30% Co;
La between about 0.5 wt% and about 2 wt%; and Ru between about 0.03 wt% and about 0.3 wt%,
A catalyst composition comprising: A method of treating a catalyst support, comprising: contacting a support material with an anti-wear composition comprising monosilicic acid to provide a treated catalyst support thereby. 24. The method of claim 23, wherein the treated catalyst support has a surface concentration between about 0.1 Si atoms / nm < ² > and about 10.60 Si atoms / nm < ² >. 24. The method of claim 23, wherein the anti-wear composition comprises between about 0.02% and about 5.4% Si by weight. 24. The method of claim 23, wherein the anti-wear composition comprises between about 0.2% and about 5.4% Si by weight. 24. The method of claim 23, wherein the anti-determination composition is prepared by contacting silicate and water under acidic conditions. 28. The method of claim 27, wherein the silicate comprises monosilicic acid. 30. The method of claim 28, wherein the monosilicic acid is prepared by contacting tetraethoxysilane and water under acidic conditions. 28. The method of claim 27, wherein the silicate is sodium orthosilicate or sodium metasilicate and has a pH of about 1.5 to about 3.5 at a temperature in the range of about 0C to about 5C. The method that is the range. 28. The method of claim 27, wherein the anti-wear composition is added to the catalyst support at a temperature in the range of about 0 ° C to about 95 ° C. 28. The method of claim 27, wherein the temperature ranges from about 0 ° C to about 10 ° C. 28. The method of claim 27, wherein the anti-wear composition comprises a polysilicic acid species, wherein the monosilicic acid concentration is greater than the concentration of higher order polymers of trisilicic acid and silicic acid. Big, way. 30. The method of claim 28, wherein the monosilicic acid is the primary silicic acid species in the antiwear composition. 24. A method according to claim 23, wherein the carrier material is preformed. A catalyst composition suitable for use in a Fischer-Tropsch process, comprising a mixture or reaction product of:
An abrasion resistant carrier prepared by contacting the carrier material with an antiwear composition comprising monosilicic acid;
cobalt;
A modifying agent selected from the group consisting of Ca, Sc, Ba, La, Hf, and combinations thereof; and at least selected from the group consisting of Ru, Rh, Pd, Re, Ir, Pt, and combinations thereof, A kind of activator. 40. The catalyst composition of claim 36, wherein the composition is substantially free of particles having a diameter of less than about 20 [mu] m under typical Fischer-Tropsch reaction conditions. 37. The catalyst composition of claim 36, wherein the support material is selected from the group consisting of Group III, Group IV, Group V, Group VI, and Group VIII refractory oxides and mixtures thereof. Catalyst composition. 37. The catalyst composition of claim 36, wherein the support material comprises aggregated gamma alumina. 37. The catalyst composition of claim 36, wherein the first transition metal is cobalt and the second transition metal is ruthenium. 37. A catalyst composition according to claim 36, wherein the support material is preformed. Fischer-Tropsch product comprising:
Paraffin wax; and gamma alumina particles having a diameter of less than about 20 nm of less than about 50 ppm, wherein the concentration of gamma alumina particles is determined following primary filtration,
Fischer-Tropsch product comprising 43. A Fischer-Tropsch product according to claim 42, wherein the Fischer-Tropsch product is made using a regenerated Fischer-Tropsch catalyst. A method for reducing the occurrence and severity of catalyst attrition comprising the following steps:
Depositing about 0.1 to about 10.6 Si per 1 nm ^{2 of} support surface area on the catalyst support surface, wherein the Si atoms bind to the support surface via oxygen atoms The process,
Including the method. 45. The method of claim 44, wherein the silicon is deposited on a support material at a concentration between about 0.55 Si / nm ² and about 5.0 Si / nm ² . 45. The method of claim 44, wherein the silicon is deposited on a support material at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ² . 45. The method of claim 44, wherein the carrier material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, zirconia, group III, group IV, group V, A process selected from the group consisting of refractory oxides of Group VI and Group VIII elements and mixtures thereof. 48. The method of claim 47, wherein the support material is aggregated gamma alumina. 48. The method of claim 47, wherein the support material is alumina bonded titania. A method for reducing the occurrence and severity of catalyst attrition comprising the following steps:
Depositing about 0.1 to about 10.6 Si per nm ^{2 of} support surface area on the catalyst support surface, wherein less than about 10 wt% silicon is in polymer form,
Including the method. 51. The method of claim 50, wherein the silicon is deposited on a support material at a concentration between about 0.55 Si / nm ² and about 5.0 Si / nm ² . 51. The method of claim 50, wherein the silicon is deposited on a support material at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ² . 51. The method of claim 50, wherein the carrier material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, zirconia, group III, group IV, group V, A process selected from the group consisting of refractory oxides of Group VI and Group VIII elements and mixtures thereof. 54. The method of claim 53, wherein the support material is aggregated gamma alumina. 54. The method of claim 53, wherein the support material is alumina bonded titania. 51. The method of claim 50, wherein less than about 5 wt% silicon is present in polymeric form. 51. The method of claim 50, wherein less than about 2.5 wt% silicon is present in polymeric form. A method for reducing the occurrence and severity of catalyst support material disassembly comprising the following steps:
Depositing about 0.1 to about 10.6 Si per 1 nm ^{2 of} support surface area on the catalyst support surface, wherein the Si atoms bind to the support surface via oxygen atoms The process,
Including the method. 59. The method of claim 58, wherein the silicon is deposited on a support material at a concentration between about 0.55 Si / nm ² and about 5.0 Si / nm ² . 59. The method of claim 58, wherein the silicon is deposited on a support material at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ² . 59. The method of claim 58, wherein the carrier material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, zirconia, group III, group IV, group V, A process selected from the group consisting of refractory oxides of Group VI and Group VIII elements and mixtures thereof. 62. The method of claim 61, wherein the support material is aggregated gamma alumina. 62. The method of claim 61, wherein the support material is alumina bonded titania. A method for reducing the occurrence and severity of catalyst support material disassembly comprising the following steps:
Depositing about 0.1 to about 10.6 Si per nm ^{2 of} support surface area on the catalyst support surface, wherein less than 10 wt% silicon is in polymer form,
Including the method. 65. The method of claim 64, wherein the silicon is deposited on a support material at a concentration between about 0.55 Si / nm ² and about 5.0 Si / nm ² . 65. The method of claim 64, wherein the silicon is deposited on a support material at a concentration between about 0.7 Si / nm ² and about 3.5 Si / nm ² . 65. The method of claim 64, wherein the support material is γ alumina, η alumina, θ alumina, δ alumina, ρ alumina, anatase titania, rutile titania, magnesia, zirconia, group III, group IV, group V, A process selected from the group consisting of refractory oxides of Group VI and Group VIII elements and mixtures thereof. 68. The method of claim 67, wherein the support material is aggregated gamma alumina. 68. The method of claim 67, wherein the support material is alumina bonded titania. 65. The method of claim 64, wherein less than about 5 wt% silicon is present in polymeric form. 65. The method of claim 64, wherein less than about 2.5 wt% silicon is present in polymer form.

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